CN103613092B - A kind of preparation method of boron doped graphene - Google Patents
A kind of preparation method of boron doped graphene Download PDFInfo
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- CN103613092B CN103613092B CN201310556311.1A CN201310556311A CN103613092B CN 103613092 B CN103613092 B CN 103613092B CN 201310556311 A CN201310556311 A CN 201310556311A CN 103613092 B CN103613092 B CN 103613092B
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Abstract
The invention provides a kind of preparation method of boron doped graphene, utilize silicon carbide high temperature thermal decomposition legal system for Graphene, doped with boron in wherein said silicon carbide.Preparation method provided by the invention is simple, safe, controlled, and prepared graphene-structured integrity is high, and boron uniform doping is good.
Description
Technical field
The present invention relates to a kind of preparation method of boron doped graphene, particularly relate to a kind of method preparing boron doped graphene based on silicon carbide high temperature thermal decomposition method.
Background technology
Graphene is a kind of novel two-dirnentional structure material.The energy band structure of its uniqueness, excellent electric property, physical strength, good chemical stability etc. make Graphene in electron device, flexible conductive film, energy storage and photochemical catalysis etc. are many, have unique advantage, become the focus of current condensed matter physics and materials science research.
Intrinsic Graphene band gap is zero, limits its application on some electron device.So the electronic structure of the band gap and regulation and control Graphene of opening Graphene becomes the prefered method advancing Graphene widespread use.Realize the regulation and control to Graphene band gap by doping, and the regulation and control realizing carrier concentration and polarity are the effective ways generally admitted at present.In theory, in Graphene lattice, mix the energy band structure that a certain amount of boron (B) atom can regulate Graphene, fermi level is lowered, form P type doped graphene, thus realize the unipolar device of Graphene.Boron doped Graphene can increase the density of states(DOS) near Fermi surface in addition, improves carrier concentration, strengthens the electroconductibility of Graphene.
The people such as C.N.R.Rao are with borine (B
2h
6) as boron source, prepare boron doped Graphene (Adv.Mater.21 (2009) 4726) by the method for graphite electrode arc electric discharge.Yellow rich and powerful, woods sky congruence utilizes active metal and low-carbon (LC) halohydrocarbon (as trichloromethane, tetracol phenixin), boron source (as boron tribromide, diborane); react in a kettle. under protection of inert gas; synthesis boron doped graphene, then to its purify (ZL201010570879.5).
But at present report most method or use poisonous and hazardous hazardous substance, or complex process, product are pure not.
Summary of the invention
Therefore, the object of the invention is to the defect overcoming above-mentioned prior art, a kind of simple, safety is provided, controllably prepare the method for high quality boron doped graphene.
The invention provides a kind of preparation method of boron doped graphene, utilize silicon carbide high temperature thermal decomposition legal system for Graphene, doped with boron in wherein said silicon carbide.
According to method provided by the invention, wherein said silicon carbide is crystal.
According to method provided by the invention, wherein said silicon carbide is silicon carbide wafer, silicon carbide powder or silicon carbide block.
According to method provided by the invention, the doping content of wherein said boron is 10
17~ 10
21cm
-3.
According to method provided by the invention, the temperature that wherein said silicon carbide high temperature thermal decomposition method uses is set to Si atom is overflowed from doped with the silicon carbide of boron, leaves carbon atom and boron atom is assembled into boron doped graphene.
According to method provided by the invention, the scope of wherein said temperature is 1300 DEG C-2200 DEG C.
According to method provided by the invention, wherein said silicon carbide high temperature thermal decomposition method is carried out in vacuum environment.
According to method provided by the invention, wherein said silicon carbide high temperature thermal decomposition method is carried out in rare gas element.
According to method provided by the invention, the treatment time of wherein said silicon carbide high temperature thermal decomposition method is 5 minutes-24 hours.
The boron doped graphene that the present invention also provides a kind of aforesaid method to prepare.
Preparation method provided by the invention is simple, safe, controlled, and prepared graphene-structured integrity is high, and boron uniform doping is good.Utilize the preparation-obtained Graphene of the method can be widely used in the investigation and application in the fields such as dye sensitization solar battery, transparency conductive electrode, ultracapacitor, field emmision material, optic catalytic composite material, biological adsorption and analysis.
Accompanying drawing explanation
Referring to accompanying drawing, embodiments of the present invention is further illustrated, wherein:
The Raman that Fig. 1 is the boron doped graphene material prepared by the method for embodiments of the invention 1 composes;
Fig. 2 is the SEM X rays topographs of the boron doped graphene material prepared by the method for embodiments of the invention 1;
Fig. 3 is the AFM X rays topographs of the boron doped graphene material prepared by the method for embodiments of the invention 3.
Embodiment
Silicon carbide high temperature thermal decomposition method is a kind of conventional method preparing Graphene, and the method utilizes saturation steam pressure reduction higher between C, Si, at high temperature heats SiC crystal, and make Si atom depart from SiC crystal, remaining C spontaneity reconfigures formation Graphene.The advantage of this method is that Graphene can be grown directly upon on semi-insulated substrate, just directly can carry out device preparation without the need to carrying out transfer.This kind of method and existing microelectronic process engineering compatibility, be considered to the preparation method being hopeful most to realize Graphene scale operation.
The invention provides a kind of method preparing boron doped graphene based on SiC high temperature thermal decomposition method.In preparation method provided by the invention, utilize the saturated vapor pressure of silicon relatively high, and the character that the saturated vapor pressure of carbon and boron is relatively low, by high temperature heating boron doped SIC material, Siliciumatom is overflowed, and the carbon atom stayed becomes boron doped Graphene with boron atom assemble in situ.
In order to make object of the present invention, technical scheme and advantage clearly understand, below in conjunction with specific embodiment, the present invention is described in more detail.Should be appreciated that specific embodiment described herein only in order to explain the present invention, be not intended to limit the present invention.
Embodiment 1
The present embodiment provides a kind of preparation method of boron doped graphene, comprising:
1) provide boron doped SIC wafer, this wafer thickness 350 μm, boron doping concentration is 5 × 10
19cm
-3.
2) acetone, dehydrated alcohol ultrasonic cleaning boron doped silicon carbide wafer is adopted successively, and clean by washed with de-ionized water, to remove the organism on SiC wafer surface.Then the further ultrasonic cleaning of dilute hydrochloric acid, diluted hydrofluoric acid is used, and clean by washed with de-ionized water, to remove metallic impurity and the silicon-dioxide zone of oxidation on SiC wafer surface.Finally the boron doped SIC wafer nitrogen after cleaning is dried up.
3) cleaned boron doped SIC wafer is placed in high-temperature heater, utilizes mechanical pump and molecular pump to bleed process to furnace chamber, make the vacuum tightness of the furnace chamber of high-temperature heater reach 5 × 10
-3pa, makes high-temperature heater be warming up to 1800 DEG C simultaneously, and this temperature 15 hours, the Si atom in SiC wafer is overflowed, and the C atom stayed became boron doped Graphene with B atom assemble in situ.At 1800 DEG C, insulation can make 350 μm of thick SiC wafer carbonizations for 15 hours, that is, make SiC wafer be transformed into boron doped Graphene completely.
4) in furnace chamber, inject argon gas to 10kPa, Temperature fall is to room temperature.Boron doped graphene material is taken out from high-temperature heater.
The Raman spectrum of boron doped graphene material prepared by the present embodiment as shown in Figure 1, therefrom clearly can see characteristic peak: G peak is (at 1582cm
-1) and 2D peak (at 2700cm
-1).Wherein 2D peak is than G peak height, and 2D symmetry of peak is good, and the Graphene prepared by explanation has the attribute of single-layer graphene.Far Left has a more weak D peak, illustrates that the defect of Graphene is few.
Boron doped graphene material SEM(scanning electronic microscope prepared by the present embodiment) X rays topographs as shown in Figure 2, wherein the degree of crystallinity of graphene film is better as seen, and graphene film is standing upright direction.
The SIMS(SIMS analysis of boron doped graphene material prepared by the present embodiment) test result shows, the boron doping concentration of this Graphene is 9 × 10
18cm
-3.
Embodiment 2
The present embodiment provides a kind of preparation method of boron doped graphene, comprising:
1) provide boron doped SIC wafer, this wafer thickness 350 μm, boron doping concentration is 5 × 10
19cm
-3.
2) acetone, dehydrated alcohol ultrasonic cleaning boron doped silicon carbide wafer is adopted successively, and clean by washed with de-ionized water, to remove the organism on SiC wafer surface.Then the further ultrasonic cleaning of dilute hydrochloric acid, diluted hydrofluoric acid is used, and clean by washed with de-ionized water, to remove metallic impurity and the silicon-dioxide zone of oxidation on SiC wafer surface.Finally the boron doped SIC wafer nitrogen after cleaning is dried up.
3) cleaned boron doped SIC wafer is placed in high-temperature heater, utilizes mechanical pump and molecular pump to bleed process to furnace chamber, make the vacuum tightness of the furnace chamber of high-temperature heater reach 5 × 10
-3pa, makes high-temperature heater be warming up to 1800 DEG C simultaneously, and this temperature 12 hours, the Si atom in SiC wafer is overflowed, and the C atom stayed became boron doped Graphene with B atom assemble in situ.At 1800 DEG C, insulation can make 350 μm of thick SiC wafer partially carbonized for 2 hours, obtains the boron doped graphene be positioned in SiC wafer.
4) in furnace chamber, inject argon gas to 10kPa, Temperature fall is to room temperature.The boron doped graphene material be positioned in SiC wafer is taken out from high-temperature heater.
The SIMS test result of boron doped graphene material prepared by the present embodiment shows, the boron doping concentration of this Graphene is 9 × 10
18cm
-3.
Embodiment 3
The present embodiment provides a kind of preparation method of boron doped graphene, comprising:
1) provide the boron doped SIC wafer through chemically machinery polished, boron doping concentration is 5 × 10
17cm
-3.
2) acetone, dehydrated alcohol ultrasonic cleaning boron doped silicon carbide wafer is adopted successively, and clean by washed with de-ionized water, to remove the organism on SiC wafer surface.Then the further ultrasonic cleaning of dilute hydrochloric acid, diluted hydrofluoric acid is used, and clean by washed with de-ionized water, to remove metallic impurity and the silicon-dioxide zone of oxidation on SiC wafer surface.Finally the boron doped SIC wafer nitrogen after cleaning is dried up.
3) cleaned boron doped SIC wafer is placed in high-temperature heater, utilizes mechanical pump and molecular pump to bleed process to furnace chamber, make the vacuum tightness of the furnace chamber of high-temperature heater reach 5 × 10
-3pa, then injects argon gas to 10kPa in furnace chamber.
4) make high-temperature heater be warming up to 1400 DEG C, make furnace chamber be evacuated to 100Pa simultaneously, this temperature 10 minutes, the Si atom in SiC wafer is overflowed, and the C atom stayed became boron doped Graphene with B atom assemble in situ.Then in furnace chamber, argon gas is injected to 10kPa.Temperature fall, to room temperature, takes out boron doped graphene material from high-temperature heater.
The AFM(atomic force microscope of boron doped graphene material prepared by the present embodiment) X rays topographs as shown in Figure 3, wherein the degree of crystallinity of graphene film is better as seen.In the preparation method that the present embodiment provides, because heat-up time is shorter, ambient pressure is higher, what obtain is the thin graphene tiled on silicon carbide substrates.The Graphene of this tiling is very suitable for the application of graphene electronic device aspect.
The SIMS test result of boron doped graphene material prepared by the present embodiment shows, the boron doping concentration of this Graphene is 6 × 10
17cm
-3.
According to other embodiments of the invention, the boron doped SIC wafer wherein in above-described embodiment also can replace with boron doped SIC powder, or other crystalline form of boron doped SIC, as boron doped SIC monocrystalline or the polycrystalline of bulk.
According to other embodiments of the invention, wherein boron doped SIC crystal can be such as the mixture of single crystal form in 4H, 6H, 3C or these crystal formations.
According to other embodiments of the invention, wherein in boron doped SIC crystal, the doping content of boron is preferably 10
17~ 10
21cm
-3.Those skilled in the art also can Graphene boron doping concentration according to actual needs and arrange the doping content of boron in boron doped SIC crystal neatly.
According to other embodiments of the invention, in the process forming boron doped graphene, the pressure of furnace chamber is not limited to the pressure described in above-described embodiment, and the pressure in furnace chamber is preferably 1 × 10
-5between Pa-1kPa.Atmosphere in furnace chamber is vacuum or rare gas element, as argon gas.
According to other embodiments of the invention, the temperature of formation boron doped graphene is not limited to the temperature described in above-described embodiment, and preferred temperature is 1300 DEG C-2200 DEG C usually.The high-temperature heating treatment time is preferably 5 minutes-24 hours, but and nonrestrictive, those skilled in the art can boron doped graphene according to actual needs thickness and adjust heat-up time.
In method provided by the invention, by regulating annealing temperature, annealing time and ambiance, and obtain being laid in SiC crystal surface, standing upright is on SiC crystal surface, or the free Graphene without substrate supports of carbonization.The thickness of Graphene can also be controlled in addition, such as, thick-layer from the thin layer of several atomic shell to tens layers by the control of the processing parameter to preparation.
The invention provides a kind of method preparing boron doped graphene based on SiC high temperature thermal decomposition method.By will in SiC crystal doped with boron, and make doped with boron in the Graphene finally prepared.Concrete technology parameter described in above-described embodiment is also nonrestrictive, and those skilled in the art can regulate processing parameter flexibly according to the character of the equipment used in reality and required obtained Graphene.The concrete technology parameter that SiC high temperature thermal decomposition method of the prior art uses all can be applicable to the present invention.
Preparation method provided by the invention has the following advantages:
1) chemical purity is high.At high temperature, O, N and other metallic impurity are all easily removed automatically.
2) graphene-structured integrity is high.This is because carbon atom is good by the restricted space distributing homogeneity of SiC structure, along with the effusion of Siliciumatom, remaining carbon and the easy in-situ junction of boron atom synthesize perfect Graphene.
3) SiC material by choosing different boron doping concentration realizes the Graphene of the different boron doping concentration of preparation.And boron uniform doping is good, not easily forms localized clusters.
4) mass-producing preparation and industrialization production is easily realized.
The method preparing boron doped graphene provided by the invention, in fields such as electron device, transparency conductive electrode, solar cell, ultracapacitor, field emmision material, matrix material, sensing, absorption, catalysis, bioanalysiss, is with a wide range of applications.
It should be noted last that, above embodiment is only in order to illustrate technical scheme of the present invention and unrestricted.Although with reference to embodiment to invention has been detailed description, those of ordinary skill in the art is to be understood that, modify to technical scheme of the present invention or equivalent replacement, do not depart from the spirit and scope of technical solution of the present invention, it all should be encompassed in the middle of right of the present invention.
Claims (7)
1. a preparation method for boron doped graphene, utilizes silicon carbide high temperature thermal decomposition legal system for Graphene, and doped with boron in wherein said silicon carbide, the doping content of described boron is 10
17~ 10
21cm
-3, the temperature range that described silicon carbide high temperature thermal decomposition method uses is 1300 DEG C-2200 DEG C.
2. method according to claim 1, wherein said silicon carbide is crystal.
3. method according to claim 1, wherein said silicon carbide is silicon carbide wafer, silicon carbide powder or silicon carbide block.
4. method according to claim 1, the temperature that wherein said silicon carbide high temperature thermal decomposition method uses is set to Si atom is overflowed from doped with the silicon carbide of boron, leaves carbon atom and boron atom is assembled into boron doped graphene.
5. method according to claim 1, wherein said silicon carbide high temperature thermal decomposition method is carried out in vacuum environment.
6. method according to claim 1, wherein said silicon carbide high temperature thermal decomposition method is carried out in rare gas element.
7. method according to claim 1, the treatment time of wherein said silicon carbide high temperature thermal decomposition method is 5 minutes-24 hours.
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| CN105217604B (en) * | 2014-06-30 | 2017-03-15 | 中国科学院物理研究所 | A kind of method of extending and growing graphene PN junction in situ on the carborundum of semi-insulating silicon face |
| CN104108712B (en) * | 2014-07-25 | 2016-01-20 | 深圳新宙邦科技股份有限公司 | A kind of boron doped graphene and preparation method thereof |
| CN107954418A (en) * | 2017-12-29 | 2018-04-24 | 北京华进创威电子有限公司 | A kind of multi-disc carborundum pyrolytic graphite alkene preparation method |
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